Motjrs



Patented Dec. 17, 1929 iii A s'rArs PTENT OFFICE JOHN H. SACHS, OF WILMINGTON, DELAWARE, ASSIGNOR '10 E. I. DU FONT NE- MOURS & COMPANY, OF WILIMINGTON, DELAWARE, A CORPORATION OF DELAWARE PRODUCTION Oh CHLOBO DERIVATIVES OF ND]iHYDRO-1,2.2",1'-ANTHRAQUINONE-AZINE No Drawing.

This invention relates .to a process of i producing chloroderivatives of N-dihydro- 1,2,2,l-ontl1raquinone-azine, and in general comprises subjecting said anthraquinoneazine preferably while suspended in sulfuric acid to the action oi nitric and hydrochloric acids freshly formed in the re ction mixture.

The chief object of my inventionis to provide a more easily controlled method of chlorinating the anthraquinonc-azine than that heretofore known. Various other objects and advantages of my invention however will be apparant from the following specification.

I have discovered that if N-dihydro- 1,2,2,1-anthraquinone-azine, in a line state of subdivision, is suspendedin sulfuric acid of, for example, 50 to 55% strength, to which the required amount of sodium nitrate has been added, and the mixture heated to a moderate temperature say, to 50 C.-an easily controlled chlorination ot the azinc may be obtained by the gradual addition ot sodium chloride. By this procedure, the anthraquinone-azineis subjected to the action of nitric and hydrochloric acids formed in the reaction mixture, the resulting oxidation and chlor ination occuring, at least to some extent, concurrently.

The invention may be illustrated in greater detail by he following examples. although, as will be understood, the invention is not limited to the particular conditions specified therein:

1. parts of.finely ground N-dihydro- 1,2,2,1-anthraqninoneazine are added slowly and with stirring to 120 parts of 52% sulfuric acid to which has been added at ordinary temperature 10 parts of dry sodium nitrate. The temperature of the mass is raised to -Zl5 G. and at this point parts of salt (NaOl) are added over a period of 3 hours. After one more hour the mass is drowned in water and filtered. The product after being washed rivative Application filed 3111;.29, 1925. Serial No. 46,882.

saltand acid-free, and then dried, contains from 5 to 6% of chlorine.

2. 10 parts of N-dihydro-l,2,2,l'-anthraquinone-azine, in the form of a paste containing solids, are run slowly and with stirring into 80 parts of 78% sulfuric acidto which has been added at ordinary temperatures 10 parts of dry sodium nitrate. The mixture is further diluted with 10 parts of watc' and then at a temperature of 50 G, 2-30 parts of salt (sodium chloride) are addedover aperiod of four hours. The mass is allowed to agitate'for another two hours after which it is drowned in Water and filtered. The product after being Washed saltand acid-tree,'and then dried, contains from 9 to 10% of chlorine.

The reaction by which chlorine is introduced into the molecule by the method described above, proceeds in two stages. The first stage is the oxidation of N-dihydro- 1,2,2,1-anthraquinone-azine to 1,2,2',1-antlp-aquinone-azine. In the second stage the latter compound, just as do other azines, adds hydrogm chloride, with theformati'on of mono-clilor N dihydro-1,2,2' ,lanthraquinone-azine. It will, of course, be understood that occasionally by reason of the simultaneous presence of hydrochloric and nitric acids in the reaction mixture a strongly oxidizing solution is obtained, as the result of which the chlorinated derivative of the N-dihydro-1,2,2,1-anthraquinone-azine is 0xidized to the corresponding chlorinated deof 1,2,2',1 anthraquinone azine. lVhere the chlorination of the N-dihydro- 1,2,2,1-anthraquinone-azine takes place with the formation of the resulting oxidized compound, it is easily possible to obtain the re duced compound, is. chlorinated N-dihydro- 1,2,2,l-anthraquinone-azine by a simple treatment of the oxidized compound with any well known reducing agent. By the oxi dation of the mono-chlor-eompound and subsequent addition of hydrogen chloride, metal chloride toform hydrogen chloride the dichloro-compound may be produced.

which will combine with the oxidized azine The graphical chemical formulas of the present.

products taking part in this process are prob- 5 ably as follows:

. v Q Ndihydro-1,2.2',1-dianthmquinone-azine The position of the chlorine atoms in the chlorinated product is not definitely known, but it is believed that in the mono-chloro 2 compound the chlorine is in the position designated by (a) .in the following formula, and that in the dichloro derivative the chlorine occupies the and (b): L p 5 00 a tages especially when the process is practiced on a large, or plant, scale. .Thus', the handling of hydrochloric and nitric acids in carboys is done away with, the cost of the materials required to chlorinate is reduced by about 40%, the cooling ofthe mixed acids is eliminated, and finally the process as carried out permits of an easy control in the amount of chlorine introducedinto the anthraquinone-azine in that this factor can be varied by the rate of addition of the salt.

Suitable changes may be made in details of operation and substances used for carry-' ing out the process, without departing from the spirit and scope of the inventim.

' I claim:

1. The process of chlorinating N-dihydro l,2,2,1-anthraquinone-- azine which comprises suspending said anthraquinone-azine in sulphuric acid containing nitric acid, and subjecting the suspended azine to-the action of hydrogen chloride formed in the reaction mixture. V

1 2. The proce'sswhich comprises adding a metal nitrate to sulphuric acid of more than 45% strength, mixing therewith finely divided N dihydfo l,2,2,l anthraquinoneazine, heating the mixture to a temperature of from about 45 to 0., and adding a positions designated by (a).

This new procedure entailsmany advan- 8. The process which. comprises mixing 1,2,2,1'-dlanthraquinone-azine I oxidized product an alkali-metal nitrate with sulphuric acid, maintaining the temperatureof the mixture at about 4550 C; while gradually adding sufiicient alkali-metal chloride to efiect chlorination of the azine, and then when the re- N-dihydro-1,2,2,1'-anthraquinone-azine and action has proceeded to the desired extent, 1 I

drowning the mass in water.

4. The process which comprises mixing N-dihydro-1,2,2f,1-anthraquinone-azine and an alkali-metal nitrate with sulphuric acid,

and maintaining the temperature of the mixtu-re at about 5t5-50 C. while graduallyadding suflicient alkali-metal chloride to efiect chlorination. of the azine.

5. The process of producing chloro-derivatives of N -dihydro-1,2,2,1anthraquinon'eazine which comprises subjecting an oxidized N-dihydro-l,2,2,l-anthraquinone-azine to the action of hydrogen chlorine formed in the reaction mixture acid. l

6. The process which comprises mixing 10 parts of N-dihydro-1,2,2,1-anthraquinoneazine and about 10 parts of sodium nitrate with sulphuric acid of moderate strength, heating the mixture to a temperature a little above normal room temperature and then gradually adding from about 20 to 30 parts oi" =odium chloride over a period of several hours to form a chloro-derivative of N-dihydro-1,2,2,1'-anthraquinone-azine.

7. The process which comprises mixing 10 parts of N -dihydro-1,2,2,1-anthraquinoneazine and about '10 parts of sodium nitrate with sulphuric acid of from between 45 and 80% strength, heating the mixture to a tem perature of about 45 C., and gradually adding sufiicient chloride to said mixture, whileters, which comprises treating an anthra-f quinonazlnewith sodlum halide in the pres.

ence of sulfuric acid.

presence of in the presence of sulphuric 10. The process of producing coloring matters, which comprises treating an anthraquinon-azine With a chloride in the presence of sulfuric acid.

11. The process of producing a chlorinated derivative of N-dihydro-1,2,2',1-anthraquinone-azine, which comprises inducing a re action between an anthraquinoneazine and hydrogen chloride in presence of sulfuric acid.

12. The process of producing a chlorine derivative of 13,2,1-anthraquinone-azine,

which comprises oxidizing an indanthrene to its corresponding azine by means of a suitable oxidant in the presence of sulfuric acid and subsequently subjecting the azine thus produced, and while still in the presence of sulfuric acid, to the action of a chloride.

13. The process ofiproducing a nionochlor derivative of 12,2,1-anthraquinone-azine,

which comprises treating 1,2,2',1-anthraquinone-azine in the presence of sulfuric acid with a chloride.

14. The process of producing a monochlor derivative of 1,2,9.,1'-anthraquinone-azine, which comprises treating 1,2,2,1-anthraquinone azine with sodium chloride in the presence of sulfuric acid.

In testimony whereof I afiix my signature. JOHN H. SACHS. 

